Surfactants and methods of making and using same

ABSTRACT

Anionic surfactants have a formula: 
       R f SO 2 N(H)—CH 2 CH(CH 3 )OH; or
 
       R f SO 2 N(H)—(CH 2 CH 2 O) x H, where  x  is an integer from 2-6. R f  is a fluoroalkyl group having 3 to 8 carbon atoms. Neutral surfactants having a formula:
 
       R f SO 2 N[CH 2 CH(CH 3 )OH] 2 ;  (a)
 
       R f SO 2 N[CH 2 CH(CH 3 )OH][(CH 2 CH 2 O) n H], where  n  is an integer from 1-6;  (b)
 
       R f SO 2 N(R)[(CH 2 CH 2 O) p H], where  p  is an integer from 2-6, and R is an alkyl group having 1 to 4 carbon atoms; or  (c)
 
       R f SO 2 N[(CH 2 CH 2 O) q H][(CH 2 CH 2 O) m H], where  q  is an integer from 1-6 and  m  is an integer from 3-6. R f  is a fluoroalkyl group having 3 to 8 carbon atoms.  (d)

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/262,678, filed Sep. 16, 2016, now allowed, which was a continuationof U.S. application Ser. No. 14/763,841, filed Jul. 28, 2015, issued asU.S. Pat. No. 9,454,082, which was a national stage filing under 35U.S.C. 371 of PCT/US2014/010769, filed Jan. 9, 2014, which claimspriority to U.S. Provisional Application No. 61/757,790 filed Jan. 29,2013, the disclosure of which is incorporated by reference in its/theirentirety herein.

FIELD

The present disclosure relates to fluorinated surfactants, and methodsof making and using the same.

BACKGROUND

Various fluorinated surfactants are described, for example, in U.S. Pat.Nos. 4,089,804 and 7,741,260, U.S. Patent Application Pub. Nos.2008/0299487 and 2008/0280230, and V. Huang et al., Proc. of SPIE, Vol.6519, 65193C-1 (2007).

SUMMARY

In some embodiments, anionic surfactants are provided. The anionicsurfactants have a formula:

R_(f)SO₂N(H)—CH₂CH(CH₃)OH; or

R_(f)SO₂N(H)—(CH₂CH₂O)_(x)H, where x is an integer from 2-6. R_(f) is afluoroalkyl group having 3 to 8 carbon atoms.

In some embodiments, neutral surfactants are provided. The neutralsurfactants have a formula:

R_(f)SO₂N[CH₂CH(CH₃)OH]₂;  (a)

R_(f)SO₂N[CH₂CH(CH₃)OH][(CH₂CH₂O)_(n)H], where n is an integer from1-6;  (b)

R_(f)SO₂N(R)[(CH₂CH₂O)_(p)H], where p is an integer from 2-6, and R isan alkyl group having 1 to 4 carbon atoms; or  (c)

R_(f)SO₂N[(CH₂CH₂O)_(q)H][(CH₂CH₂O)_(m)H], where q is an integer from1-6 and m is an integer from 3-6. R_(f) is a fluoroalkyl group having 3to 8 carbon atoms.  (d)

In some embodiments, fluorinated sulfonamide surfactant compositions areprovided. The compositions include an anionic surfactant according tothe formula:

R_(f)SO₂N(H)—CH₂CH(CH₃)OH; or

R_(f)SO₂N(H)—(CH₂CH₂O)_(x)H, where x is an integer from 2-6; or aneutral surfactant according to the formula:

R_(f)SO₂N[CH₂CH(CH₃)OH]₂;

R_(f)SO₂N[CH₂CH(CH₃)OH][(CH₂CH₂O)_(n)H], where n is an integer from 1-6;

R_(f)SO₂N(R)[(CH₂CH₂O)_(p)H], where p is an integer from 2-6, and R isan alkyl group having 1 to 4 carbon atoms; or

R_(f)SO₂N[(CH₂CH₂O)_(q)H][(CH₂CH₂O)_(m)H], where q is an integer from1-6, m is an integer from 1-6, and (q+m)≧3; and

a solvent. R_(f) is a fluoroalkyl group having 3 to 8 carbon atoms.

In some embodiments, fluorinated sulfonamide surfactant compositions areprovided. The compositions include an anionic surfactant according tothe formula:

R_(f)SO₂N(H)—CH₂CH(CH₃)OH;

R_(f)SO₂N(H)—(CH₂CH₂O)_(x)H, where x is an integer from 2-6; or

R_(f)SO₂N(H)—CH₂CH₂OH; and

a neutral surfactant according to the formula:

R_(f)SO₂N[CH₂CH(CH₃)OH]₂;

R_(f)SO₂N[CH₂CH(CH₃)OH][(CH₂CH₂O)_(n)H], where n is an integer from 1-6;

R_(f)SO₂N(R)[(CH₂CH₂O)_(p)H], where p is an integer from 2-6 and R is analkyl group having 1 to 4 carbon atoms;

R_(f)SO₂N[(CH₂CH₂O)_(q)H][(CH₂CH₂O)_(m)H], where q is an integer from1-6, m is an integer from 1-6, and q+m≧3; or

R_(f)SO₂N[CH₂CH₂OH]₂; and

a solvent. R_(f) is a fluoroalkyl group having 3 to 8 carbon atoms. Ifthe composition comprises appreciable amounts of only one anionicsurfactant and only one neutral surfactant, and the anionic surfactantis R_(f)SO₂N(H)—CH₂CH₂OH, then the neutral surfactant is notR_(f)SO₂N[CH₂CH₂OH]₂.

The above summary of the present disclosure is not intended to describeeach embodiment of the present disclosure. The details of one or moreembodiments of the disclosure are also set forth in the descriptionbelow. Other features, objects, and advantages of the disclosure will beapparent from the description and from the claims.

DETAILED DESCRIPTION

The present disclosure describes fluorinated sulfonamide surfactants andsurfactant compositions that may be particularly useful as surfaceactive agents in aqueous solutions. The surfactants and compositions mayprovide a number of advantages relative to known surfactants, including,for example, improved water solubility, reduced surface tensions inaqueous media, controlled wetting, and controlled absorption onto orinto photoresists. Applications for the surfactants and surfactantcompositions of the present disclosure include, for example, use aswetting agents, cleaning surfactants, coating surfactants for improvedleveling and reduced coating defects, and buffered oxide etch (BOE)surfactants. An additional application for the surfactants andsurfactant compositions of the present disclosure is their use asphotoresist developer rinse surfactants used in semiconductor processingas described in U.S. Pat. No. 7,741,260; U.S. Patent Application Pub.No. 2008/0280230; and in V. Huang et al., Proc. of SPIE, Vol. 6519,65193C-1 (2007); S. Spyridon et al., Advances in Resist Technology andProcessing XXI, J. L. Sturtevant Ed., Proc. of SPIE, Vol. 5376 (SPIE,Bellingham, W A, 2004); K. Tanaka et al., Advances in Resist Technologyand Processing XX, T. Fedynyshyn, Ed., Proc. of SPIE, Vol. 5039 (2003);and O. Miyahara et al., Advances in Resist Technology and ProcessingXXI, J. L. Sturtevant Ed., Proc. of SPIE, Vol. 5376 (SPIE, Bellingham, WA, 2004).

In semiconductor processing, typically, an integrated circuit consistingof a series of patterned functional layers (insulators, metal wires,etc) is formed. The structure of each layer is transferred from a maskvia photolithography followed by etching or ion implantation. In thephotolithographic process, the functional layer is covered by aphotoresist film. The circuits are typically fabricated with achemically amplified photoresist consisting of a polymer with anacid-labile pendant protecting group, photoacid generator (PAG), andadditional additives. Upon exposure to UV radiation through a patternedmask, the PAG is decomposed, generating a low concentration of acid. Inthe post-exposure bake step, the acid diffuses and catalyzes adeprotection reaction that cleaves the pendant group of the insolublepolymer resulting in a polymer that is soluble in the developersolution. The exposed positive tone photoresist is then removed,generally using solutions including tetramethyl ammonium hydroxide,leaving a pattern of unexposed photoresist lines, or features.

The semiconductor industry is rapidly migrating towards minimal featuresize (e.g., less than 100 nm, less than 50 nm, less than 30 nm, or evenless than 20 nm). To fulfill the demands for feature size reduction,critical dimensions of the photoresist structures must shrinkadequately. Their heights cannot be reduced in the same way since etchresistance must be retained, forcing an increase in aspect ratio. Withincreasing aspect ratio, the mechanical strength of the photoresistlines decreases, leading to collapse of the structures during thedevelopment or post development processing. This pattern collapse iscaused, at least in part, by unbalanced capillary forces acting betweenthe lines after development and during the rinse and drying steps. Ithas been demonstrated that the surface tension of the rinse fluid andthe contact angle of the rinse fluid on the photoresist are keyparameters of the rinse fluid affecting pattern collapse. A promisingapproach to reduce pattern collapse is to incorporate surfactantsolutions in the development and/or post-development rinse steps of thephotolithographic process. To date, surfactant solutions have exhibitedperformance limitations when employed on very small feature sizes (e.g.,less than about 28 nm). These deficiencies generally relate to thecleaning performance of the surfactant and its impact on the melting ofresist features and defectivity (water mark and particle defects).Consequently, improved surfactant formulations that provide betterperformance for next generation high resolution wafer processing (e.g.,feature sizes of less than 28 nm, less than 22 nm, less than 20 nm, lessthan 16 nm and beyond) in photoresist developer rinse applications maybe desirable.

DEFINITIONS

As used herein, the singular forms “a”, “an”, and “the” include pluralreferents unless the content clearly dictates otherwise. As used in thisspecification and the appended embodiments, the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

As used herein, the recitation of numerical ranges by endpoints includesall numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2,2.75, 3, 3.8, 4, and 5).

As used herein, the phrase “anionic surfactants” refers to fluorinatedsulfonamide surfactants having acidic hydrogens that are readilydeprotonated in the presence of a weak or strong base to form an anionsalt of the conjugate acid. In their deprotonated form, anionicsurfactants can be paired with any cation including, for example, NH₄ ⁺and Me₄N⁺, Bu₄N⁺. The anionic surfactants of the present disclosure canexist in their neutral protic forms or as their anion salts or a mixtureof neutral and anion salt forms in solution, depending on the pH of thesolution.

As used herein, the phrase “neutral surfactants” refers to fluorinatedsulfonamide surfactants having no strongly acidic hydrogens (i.e.,pKa>10, preferably pKa>15) and, therefore, that do not readily reactwith weak or strong base in aqueous solution to form anionic species.The composition and state of charge of the neutral surfactants of thepresent disclosure may be essentially independent of pH.

As used herein, the phrase “mixed surfactant” or surfactant blends referto compositions that include at least one anionic surfactant and atleast one neutral surfactant.

Unless otherwise indicated, all numbers expressing quantities oringredients, measurement of properties and so forth used in thespecification and embodiments are to be understood as being modified inall instances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the foregoingspecification and attached listing of embodiments can vary dependingupon the desired properties sought to be obtained by those skilled inthe art utilizing the teachings of the present disclosure. At the veryleast, and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claimed embodiments, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

In some embodiments, the present disclosure describes fluorinatedsulfonamide surfactants. The fluorinated sulfonamide surfactants mayinclude an anionic surfactant having a structure as follows:

R_(f)SO₂N(H)—CH₂CH(CH₃)OH; or

R_(f)SO₂N(H)—(CH₂CH₂O)_(x)H, where x is an integer from 2-6, 2-5, 2-4,or 2-3.

Alternatively, the fluorinated sulfonamide surfactants may include aneutral surfactant having a structure as follows:

R_(f)SO₂N[CH₂CH(CH₃)OH]₂;

R_(f)SO₂N[CH₂CH(CH₃)OH][(CH₂CH₂O)_(n)H], where n is an integer from 1-6,1-5, 1-4, or 1-3;

R_(f)SO₂N(R)[(CH₂CH₂O)_(p)H], where p is an integer from 2-6, 2-5, 2-4,or 2-3, and R is an alkyl group having 1 to 4 carbon atoms; or

R_(f)SO₂N[(CH₂CH₂O)_(q)H][(CH₂CH₂O)_(m)H], where q is an integer from1-6, or 1-5, 1-4, or 1-3 and m is 3-6, 3-5, 3-4, or 3.

In some embodiments, to facilitate maximum solubility in water, at leastone of the non-fluorinated groups bound to the sulfonamide nitrogen atomof either the anionic or neutral surfactant may be an oligomericethylene oxide group, wherein the oligomeric ethylene oxide group has2-6, 2-5, 2-4, or 2-3 ethylene oxide repeat units.

In an alternative embodiment, the fluorinated sulfonamide surfactantsmay include anionic and neutral surfactants having a structure asfollows:

R_(f)SO₂N(H)—[CH₂CH(CH₃)O]_(z)H, where z is an integer from 2-6, 2-5,2-4, or 2-3; or

R_(f)SO₂N[(CH₂CH(CH₃)O)_(y)H][(CH₂CH(CH₃)O)_(j)H]; where y is an integerfrom 1-6, 1-5, 1-4, 1-3; or 1-2; and j is an integer from 2-6, 2-5, 2-4,or 2-3; or

R_(f)SO₂N[(CH₂CH(CH₃)O)_(k)H][(CH₂CH₂O)_(n)H], where n is an integerfrom 1-6, 1-5, 1-4, or 1-3; and k is an integer from 2-6, 2-5, 2-4, or2-3.

Similar anionic and neutral fluorinated sulfonamide surfactantstructures wherein the ethylene oxide and propylene oxide groups areco-oligomerized in the same chain, as exemplified in —CH₂CH₂O—CH₂CHCH₃OHor —CH₂CHCH₃O—CH₂CH₂OH, are also possible. The fluorinated sulfonamidesurfactants of the present disclosure may include such surfactants,including higher oligomers.

For the above-described fluorinated sulfonamide surfactants, each R_(f)may independently be a fluoroalkyl group having 3 to 8 carbon atoms. Thefluoroalkyl group may be straight chain, branched chain, or cyclic, andmay be saturated or unsaturated. The fluoroalkyl group chain may beinterrupted by catenary heteroatoms (e.g., O and N). The fluororoalkylgroup may have any degree of fluorination. In various embodiments, R_(f)may be a fluoroalkyl group having 4 to 6 carbon atoms. In furtherembodiments, R_(f) may be a saturated perfluoroalkyl group having 4 to 6carbon atoms. Still further, R_(f) may be a saturated perfluoroalkylgroup having 4 carbon atoms.

In some embodiments, the present disclosure describes fluorinatedsulfonamide surfactant compositions including one or more anionicsurfactants or one or more neutral surfactants, and a solvent. Suitableanionic surfactants for the surfactant compositions include those havingthe following structure:

R_(f)SO₂N(H)—CH₂CH(CH₃)OH; and

R_(f)SO₂N(H)—(CH₂CH₂O)_(x)H, where x is an integer from 2-6, 2-5, 2-4,or 2-3.

Suitable neutral surfactants for the compositions include those havingthe following structure:

R_(f)SO₂N[CH₂CH(CH₃)OH]₂;

R_(f)SO₂N[CH₂CH(CH₃)OH][(CH₂CH₂O)_(n)H], where n is an integer from 1-6,1-5, 1-4, or 1-3;

R_(f)SO₂N(R)[(CH₂CH₂O)_(p)H], where p is an integer from 2-6, 2-5, 2-4,or 2-3, and R is an alkyl group having 1 to 4 carbon atoms; and

R_(f)SO₂N[(CH₂CH₂O)_(q)H][(CH₂CH₂O)_(m)H], where q is an integer from1-6, 1-5, 1-4, or 1-3, m is an integer from 1-6, 1-5, 1-4, or 1-3, and(q+m)≧3.

To facilitate maximum solubility in water, in various embodiments, atleast one of the non-fluorinated groups bound to the sulfonamidenitrogen atom of either the anionic or neutral surfactant may be anoligomeric ethylene oxide group, wherein the oligomeric ethylene oxidegroup has 2-6, 2-5, 2-4, or 2-3 ethylene oxide repeat units.

In some embodiments, the present disclosure describes fluorinatedsulfonamide mixed surfactant compositions including at least one anionicsurfactant, at least one neutral surfactant, and a solvent. Suitableanionic surfactants for the mixed surfactant compositions include thosehaving the following structure:

R_(f)SO₂N(H)—CH₂CH(CH₃)OH;

R_(f)SO₂N(H)—(CH₂CH₂O)_(x)H, where x is an integer from 2-6, 2-5, 2-4,or 2-3; and

R_(f)SO₂N(H)—CH₂CH₂OH.

Suitable neutral surfactants for the mixed surfactant compositionsinclude those having the following structure:

R_(f)SO₂N[CH₂CH(CH₃)OH]₂;

R_(f)SO₂N[CH₂CH(CH₃)OH][(CH₂CH₂O)_(n)H], where n is an integer from 1-6,1-5, 1-4, or 1-3;

R_(f)SO₂N(R)[(CH₂CH₂O)_(p)H], where p is an integer from 2-6, 2-5, 2-4,or 2-3 and R is an alkyl group having 1 to 4 carbon atoms;

R_(f)SO₂N[(CH₂CH₂O)_(q)H][(CH₂CH₂O)_(m)H], where q is an integer from1-6, 1-5, 1-4, or 1-3, m is an integer from 1-6, 1-5, 1-4, or 1-3, and(q+m)≧3; and

R_(f)SO₂N[CH₂CH₂OH]₂.

In one embodiment, a fluorinated sulfonamide mixed surfactantcomposition may include appreciable amounts of (i.e. >5% by weight ofthe total fluorinated surfactant present on a 100% solids basis) onlyone anionic surfactant and only one neutral surfactant. In such anembodiment, if the anionic surfactant is R_(f)SO₂N(H)—CH₂CH₂OH, then theneutral surfactant is not R_(f)SO₂N[CH₂CH₂OH]₂.

For the above-described fluorinated sulfonamide surfactant compositions(including the mixed surfactant compositions), each R_(f) mayindependently be a fluroalkyl group having 3 to 8 carbon atoms. Thefluoroalkyl group may be straight chain, branched chain, or cyclic, andmay be saturated or unsaturated. The fluoroalkyl group chain may beinterrupted by catenary heteroatoms (e.g., O and N). The fluoroalkylgroup may have any degree of fluorination. In various embodiments, R_(f)may be a fluoroalkyl group having 4 to 6 carbon atoms. In furtherembodiments, R_(f) may be a saturated perfluoroalkyl group having 4 to 6carbon atoms. Still further, R_(f) may be a saturated perfluoroalkylgroup having 4 carbon atoms.

To facilitate maximum solubility in water, in various embodiments, atleast one of the non-fluorinated groups bound to the sulfonamidenitrogen atom of either the anionic or neutral surfactant may be anoligomeric ethylene oxide group, wherein the oligomeric ethylene oxidegroup has 2-6, 2-5, 2-4, or 2-3 ethylene oxide repeat units.

In some embodiments, the fluorinated sulfonamide surfactants of thepresent disclosure may include one or more of the compounds listed inTable 1. In various embodiments, the fluorinated sulfonamide surfactantcompositions of the present disclosure may include one or more of thefluorinated sulfonamide surfactants listed in Table 1.

TABLE 1 Structure #, Acronym I, H-FBSP

II, FBSPP

III, H-FBS(EE)

IV, FBS(EE)2

V, FBSE(EE)

VI, Me-FBS(EE)

VII, Pr-FBS(EE)

VIII, H-FBS(EEE)

IX, FBS(EEE)2

X, FBSPE

In various embodiments, suitable solvents for the fluorinatedsulfonamide surfactant compositions of the present disclosure mayinclude water and/or any organic solvents that provide adequatesurfactant solubility at the surfactant loading level required foracceptable performance. Single solvents or solvent mixtures may beemployed. In some embodiments, the solvent may include water and one ormore alcohol base chemicals, such as those described in U.S. PatentApplication Pub. No. 2008/0280230.

In illustrative embodiments, the fluorinated sulfonamide surfactants maybe present in solution (i.e., in water or in a mixed solvent of waterand an organic solvent) at a total concentration (i.e., all fluorinatedsulfonamide surfactant species included) of between 0.001% to 5.0% bymass, 0.01% to 1.0% by mass, or even 0.1% to 0.5% by mass.

In some embodiments, the fluorinated sulfonamide surfactant compositionsof the present disclosure may further include one or more additives tofacilitate performance in a particular application. For example, inbuffered oxide etch (BOE) applications, additives may include NH₄F andHF. As another example, in photoresist developer or developer rinseapplications, additives may include Me₄NOH, Bu₄NOH, and/or NH₄OH. Stillfurther, when used as wetting or leveling agents in coatingapplications, coating polymers and other additives may be added toimprove coating performance.

The fluorinated sulfonamide surfactants and surfactant compositions ofthe present disclosure provide a number of surprising advantagescompared to known surfactants. For example, the surfactants andsurfactant compositions of the present disclosure exhibit improved watersolubility, which can be important to reducing the possibility ofsurfactant precipitation during semiconductor processing and associateddefect formation. As a specific example, it was discovered that anionicand neutral fluorinated sulfonamide surfactants of the presentdisclosure that have oligomeric ethylene oxide groups [—(CH₂CH₂O)_(n),where n>1] bound to the sulfonamide nitrogen atom provide significantlyhigher solubility in water compared to known sulfonamide surfactants.

In various embodiments, the neutral surfactants and mixed surfactants ofthe present disclosure may exhibit surprisingly higher water solubilitythan known neutral or mixed surfactants. The neutral surfactants of thepresent disclosure may exhibit solubility in water (e.g., 18 megaohmwater, at 25° C.) of at least 0.02%, at least 0.06%, or even at least0.1%. The mixed surfactants of the present disclosure may exhibit awater solubility of at least 0.1%, at least 0.4%, or even at least 0.8%.

Additionally surprising is that the fluorinated sulfonamide surfactantsof the present disclosure provide lower surface tensions in aqueoussolution than similar surfactants and surfactant mixtures known in theart. This parameter can be important in advanced photolithographicprocesses to reducing the incidence of pattern collapse during thedevelopment or post development rinse steps. As a specific example, itwas discovered that very low surface tensions can be achieved in waterby controlling the pH of surfactant compositions comprising the anionicsurfactants of the present disclosure. pH is generally controlled withinabout ±3 pH units of the pKa of the fluorinated anionic sulfonamidesurfactant in order to achieve optimum performance. Furthermore, asynergy was discovered wherein lower surface tensions or improvedsolubilities can be achieved in water by combining the anionic andneutral surfactants of the present disclosure, relative to theindividual surfactant components alone.

In some embodiments, the neutral surfactants of the present disclosuremay exhibit a surface tension of no more than 30 dyn/cm, no more than 24dyn/cm, or even no more than 20 dyn/cm as measured using the SurfaceTension Test Method, described below; and the mixed surfactants mayexhibit a surface tension of no more than 30 dyn/cm, no more than 24dyn/cm, or even no more than 20 dyn/cm, as measured using the SurfaceTension Test Method, described below.

Further surprising is that the fluorinated sulfonamide surfactants ofthe present disclosure, when used in aqueous photoresist rinsesolutions, can provide additional flexibility in fine tuning the levelof absorption of surfactant onto or into the photoresist material. As aspecific example, it was discovered that by adjusting the pH ofsurfactant compositions that include one or more anionic surfactants ofthe present disclosure and/or altering the choice and relative ratios ofthe anionic and neutral surfactants of the present disclosure, asignificant impact on the mass of surfactant absorbed from solution ontoor into the photoresist material can be achieved. It is generally knownin the art that such surfactant absorption can affect contact angles ofaqueous rinse solutions on the resist surface, and influence keylithography performance attributes, such as defectivity (e.g.,watermarks and particle defects), line width roughness, line edgeroughness, line melting, and process window.

The present disclosure further relates to methods of making the abovedescribed fluorinated sulfonamide surfactants. In some embodiments, suchmethods may include deprotonating a fluorochemical sulfonamidecontaining at least one acidic N—H group with a base to form afluorochemical sulfonamide anion, which can then nucleophilically attackan electrophilic reagent containing a leaving group (E), as in Scheme Ibelow. Since the protons of a fluorochemical sulfonamide are acidic dueto electron withdrawal by the fluoroalkylsulfonyl group, a variety ofdifferent bases can be used to facilitate deprotonation, such as alkalimetal carbonates, organic amines, or alkali metal alkoxides. Theelectrophilic reagent can, for example, be an alkyl or polyoxyalkylhalide (where the halide is chloride or bromide or iodide), or a cyclicepoxide (like ethylene oxide or propylene oxide) or a cyclic organiccarbonate reagent (like ethylene carbonate or propylene carbonate) thatring opens, with or without oligomerization. In the case of the cyclicorganic carbonate reagents, CO₂ byproduct may be released in the courseof the ring opening reaction. Scheme I below illustrates a non-limitingexample of a process that may be used to append a polyethylene oxidechain to a fluorinated sulfonamide N atom. However, it is to beappreciated that other routes, including those described in the Examplessection of the present disclosure, may be employed.

The present disclosure further relates to methods of making the abovedescribed fluorinated sulfonamide surfactant compositions. Such methodsmay include first adding aqueous ammonia to water to form a solution.One example of a commercially suitable ammonia includes, but is notlimited to, product number 3265-45, 28-30% ammonia in water, availablefrom Mallinkrodt Chemicals. In one embodiment, the water is 18.2 MΩwater. Fluoroalkyl sulfonamide may then be charged to the solution tomake an aqueous fluoroalkyl sulfonamide solution. The solutions may bemixed for about one hour and allowed to settle overnight. The solutionmay then be filtered to remove insoluble material and particles. In oneembodiment, the filter membrane may be polytetrafluoroethylene (PTFE),polyethylene (PE), polyether sulfone (PES), or glass fiber. In oneembodiment, the filter is at least a 1 μm rating and particularly atleast a 0.2 μm rating.

Generally, a process of forming a photoresist pattern on a substrate(e.g., semiconductor wafer) may include forming a resist layer over oron the substrate or wafer. Next, the resist layer may be exposed using alithography tool, optionally followed by a post-exposure bake step.Accordingly, the desired pattern can be initially transferred to theresist layer. The method may then include developing the exposed resistlayer by immersing the substrate in or otherwise subjecting thesubstrate to a developer fluid. Optionally, the method may then includerinsing the developed photoresist material with deionized (DI) water.

In some embodiments, the present disclosure further relates to methodsof treating the surface of a photoresist material. In this regard, themethods of the present disclosure may include carrying out theabove-described developing step by incorporating the fluorinatedsulfonamide surfactants or surfactant compositions into the developerfluid. Additionally, or alternatively, the methods of the presentdisclosure may include carrying out a fluorinated sulfonamide surfactantrinse step in lieu of, prior to, or subsequent to the above-described DIwater rinsing step. The fluorinated sulfonamide surfactant rinse mayinclude one or more fluorinated sulfonamide surfactants or surfactantcompositions of the present disclosure.

The operation of the present disclosure will be further described withregard to the following detailed examples. These examples are offered tofurther illustrate the various specific and preferred embodiments andtechniques. It should be understood, however, that many variations andmodifications may be made while remaining within the scope of thepresent disclosure.

Examples Surface Tension Test Method

Surface tension was measured using a K12 process tensiometer (availablefrom Kruss GmbH of Hamburg, Germany) using a Wilhemly plate method witha platinum PL01 plate (available from Krüss GmbH). Forty milliliters ofthe solution to be tested were placed in a 60 mL glass snap cap jar withan inner diameter of approximately 1.5 inches. Measurements were takenuntil the average of five measurements had a standard deviation lessthan 0.07 dyn/cm.

TABLE 2 Structures of Examples and Comparatives* Structure #, SynAcronym Ex # I H-FBSP 1

II FBSPP 1

III H-FBS(EE) 2

IV FBS(EE)2 3

V FBSE(EE) 4

VI Me-FBS(EE) 5

VII Pr-FBS(EE) 6

VIII H-FBS(EEE) 7

IX FBS(EEE)2 7

X FBSPE 8

A H-FBSE

B FBSEE

C Me-FBSE

D FBSA

E FES(EE)2 9

*Structures of the invention have Roman numeral designations.Comparative structure examples have alphabetic letter designations.

Surfactant Synthesis Examples Synthesis 1: C₄F₉SO₂N(H)CH₂CH(CH₃)OH (I)and C₄F₉SO₂N[CH₂CH(CH₃)OH]₂ (II)

C₄F₉SO₂NH₂ (100.00 g, 0.3343 mol) (prepared as described in U.S. Pat.No. 7,169,323), K₂CO₃ powder (5.54 g, 0.0401 mol), and anhydrouspropylene carbonate (68.26 g, 0.6687 mol) were batch charged to a 200 mLround bottom flask equipped with a Claisen adapter, water cooledcondenser with nitrogen inlet line, immersion thermocouple probe,magnetic stirrer and heating mantle. The reaction mixture was graduallyheated to 160° C. under nitrogen with stirring and then held at 160° C.for about 15 hours. After cooling to room temperature, an aliquot of thereaction mixture was removed and analyzed by GC in acetone. GC-FIDanalysis revealed the presence of about 38% C₄F₉SO₂N(H)CH₂CH(CH₃)OH and24% C₄F₉SO₂N[CH₂CH(CH₃)OH]₂ (mix of two diastereomers). Peak assignmentswere confirmed by GC-MS. To the reaction mixture was added 69.4 g ofdeionized water and 19.4 g of 20 wt % H₂SO₄(aq). After heating to 60° C.to reduce viscosity the reaction mixture was stirred vigorously toneutralize all residual base and then transferred to a separatory funneland allowed to phase separate. The lower product phase was separated,washed with about 60 mL of additional hot water and then phase separatedagain. The lower product phase was isolated and then dissolved in 240 gof MTBE (methyl t-butyl ether available from Sigma-Aldrich, St Louis,Mo.) to cut viscosity and facilitate additional extractions. Afterfiltration by gravity through fluted filter paper, the product solutionin MTBE was transferred to a 1.0 L separatory funnel and extracted withthree 300 mL portions of deionized (DI) water. The upper MTBE/productphase was isolated and then concentrated on a rotary evaporator at 20Torr, 20-50° C. to remove bulk of MTBE solvent to isolate crude product.

The crude product was then fractionally distilled under vacuum (3 Torr)through a short Vigreux column to separate and isolate the two desiredproduct fractions. Fraction #2 comprising 36.4 g of 92.1% pureC₄F₉SO₂N(H)CH₂CH(CH₃)OH was collected at a head temperature of 128-133°C. Fraction #5 comprising 12.49 g of 91.7% pure C₄F₉SO₂N[CH₂CH(CH₃)OH]₂(mix of two diastereomers) was collected at a head temperature of148.0-148.5° C. The two isolated product fractions (#2 and #5) wereseparately dissolved in hot toluene to 20% solids, filtered hot toremove insolubles, and then allowed to cool to room temperature andrecrystallize. Once recrystallization was complete, the whitecrystalline solids that formed were isolated by vacuum filtration,washed with toluene at room temperature (RT) and then recrystallized asecond time from hot toluene at about 30% solids using a similarprocedure. The isolated crystalline solids were vacuum dried at 60-65°C. for about 3 hours in a vacuum oven at about 80 mTorr to removeresidual toluene and other volatiles. The final isolated yield ofC₄F₉SO₂N(H)CH₂CH(CH₃)OH from Fraction #2 was 27.082 g with a GC-FIDpurity of 98.54%. C₄F₉SO₂N(H)CH₂CH(CH₃)OH was a solid with a meltingpoint of 80.33° C. as determined by DSC. The final isolated yield ofC₄F₉SO₂N[CH₂CH(CH₃)OH]₂ from Fraction #5 was 8.537 g with a GC-FIDpurity of 99.77% (approximately 50:50 mixture of two possiblediastereomers). In both cases the only observable impurity was residualtoluene solvent. Both purified product samples were analyzed by ¹H, ¹⁹Fand ¹³C NMR spectroscopy to determine the identities and relativequantities of the primary isomeric components. The product isolated fromdistillate Fraction #2 was found to contain 98.3%C₄F₉SO₂N(H)CH₂CH(CH₃)OH (major isomer) and 1.7% C₄F₉SO₂N(H)CH(CH₃)CH₂OH(minor isomer). Fraction #5 was found to contain 99.2%C₄F₉SO₂N[CH₂CH(CH₃)OH]₂ (major isomer) and 0.8%C₄F₉SO₂N[CH₂CH(CH₃)OH][CH(CH₃)CH₂OH] (minor isomer). The NMR resultsconfirm that propylene carbonate is preferably attacked by thenucleophilic sulfonamide nitrogen at the unsubstituted, secondary —CH₂—carbon to form the major mono-ol and diol product isomers.

Synthesis 2: C₄F₉SO₂N(H)CH₂CH₂OCH₂CH₂OH (III)

C₄F₉SO₂NH₂ (100.00 g, 0.3343 mol) and triethylamine (101.48 g, 1.0029mol) were batch charged to a 500 mL, 3-necked round bottom flaskequipped with a Claisen adapter, addition funnel, water cooled condenserwith nitrogen inlet line, immersion thermocouple probe, mechanicalstirrer and heating mantle. After heating mixture to a set point of 60°C., ClCH₂CH₂OCH₂CH₂OH (53.726 g, 0.4313 mol; available from Alfa Aesar,Ward Hill, Mass.) was gradually added with stirring from addition funnelover a period of 40 minutes without significant exotherm or precipitate.Reaction temperature was increased to 95° C. and held for 17 hoursresulting in formation of significant white precipitate (Et₃NH⁺Cl⁻). GCanalysis of an aliquot of the reaction mixture indicated that thereaction had proceeded to only 36.5% conversion, so an additional 10.00g of ClCH₂CH₂OCH₂CH₂OH was charged to the reaction mixture via syringeand the mixture was allowed to react at 95° C. for an additional 66hours with stirring. After cooling to room temperature, an aliquot ofthe reaction mixture was removed for GC-FID analysis, which revealed23.1% unreacted C₄F₉SO₂NH₂, 52.2% C₄F₉SO₂N(H)CH₂CH₂OCH₂CH₂OH (desiredproduct) and 24.8% of the corresponding diol,C₄F₉SO₂N[CH₂CH₂OCH₂CH₂OH]₂. To the cooled reaction mixture was added 69g deionized water and 99.4 g of 20% H₂SO₄(aq) with stirring. Theresulting mixture was transferred to a 1.0 L separatory funnel andextracted with 239 g MTBE. The lower aqueous phase was separated anddrained and the remaining MTBE/product phase was washed with 300 mL ofdeionized water. A stable emulsion formed, which was broken by adding asmall amount of concentrated aqueous NaCl and 150 mL of 42.5% phosphoricacid. After this first wash, the lower aqueous phase was drained and theremaining MTBE phase was washed two more times with a mixture of 300 mLof water and 150 ml of 42.5% phosphoric acid. A stable emulsion wasformed again during the third wash, so entire contents of separatoryfunnel were drained into a beaker and the MTBE was allowed to evaporate.This resulted in clean phase separation of the product (lower phase)from the aqueous acid (upper phase). The lower product phase wasisolated using a separatory funnel and then purified by fractionalvacuum distillation at 2.0 Torr through a short Vigreux column. A totalof 33.9 g of desired product, C₄F₉SO₂N(H)CH₂CH₂OCH₂CH₂OH, was collectedin Fraction #3 at a head temperature of 136.5-143.5° C. The isolatedproduct collected in Fraction #3 was a clear colorless viscous liquidinitially, with a purity determined by GC-FID of 99.25%. GC peakassignments were confirmed by GC-MS. This material ultimatelycrystallized to a low melting solid with a melting point (mp) of 35.7°C.

Synthesis 3: C₄F₉SO₂N(CH₂CH₂OCH₂CH₂OH)2, (IV)

C₄F₉SO₂NH₂ (295 g, 0.9867 mol) and ClCH₂CH₂OCH₂CH₂OH (491 g, 3.94 mol)were batch charged to a 1000 mL, 3-necked round bottom flask equippedwith a Claisen adapter, water cooled condenser, immersion thermocoupleprobe, mechanical stirrer and heating mantle. After heating mixture to aset point of 90° C., potassium carbonate (300 g, 2.17 mol) was graduallyadded with stirring over a period of 15 minutes without significantexotherm or precipitate. Reaction temperature was increased to 120° C.and held for 17 hours. The batch temperature was lowered to 90° C. and1000 g of hot water was added. The contents were split in a separatoryfunnel to give 622 g of lower fluorochemical phase. The lower phase wasreturned to the flask and 300 ml of water, 107 g of 86% phosphoric acid,and 53 g of sodium chloride was added and stirred with the batch, andthen poured into a separatory funnel. The bottom layer was then splitoff to give 669 g. The lower phase was stripped at atmospheric pressureuntil the pot temperature reached 150° C. The batch was then cooled to90° C., and with good stirring the stripping was continued under vacuumto remove unreacted ClCH₂CH₂OCH₂CH₂OH and C₄F₉SO₂NH₂. Stripping wasbegun at 90° C. and 103 mm Hg to a receiver that was cooled in dryice/acetone and continued until the vacuum was 0.4 mm Hg and the batchhad reached 100° C. The batch was cooled, vacuum was broken and thereceiver was emptied. The distillation was then continued at 0.4 mm Hg.Cut 1 distilled at a head temp of 173-181° C. and a pot temp of 189-200°C., and weighed 34 g. Cut 2 distilled at 0.2 mm Hg at a head temperatureof 181-182° C. and a pot temperature of 200-203° C. and weighed 118 g.Cut 3 distilled at 0.2 mm at a head temperature of 181-210° C. and a pottemperature of 207-215° C. and weighed 47 g.

NMR and GC/MS showed cut 2 to be 89.5% the desiredC₄F₉SO₂N(CH₂CH₂OCH₂CH₂OH)₂ (including minor branched FC isomers), 9.8%C₄F₉SO₂NHCH₂CH₂OCH₂CH₂OH, 0.6% C₄F₉SO₂NH₂. GC/MS showed cut 3 to be83.1% the desired C₄F₉SO₂N(CH₂CH₂OCH₂CH₂OH)₂ (including minor branchedFC isomers).

Synthesis 4: C₄F₉SO₂N(CH₂CH₂OCH₂CH₂OH)(CH₂CH₂OH), (V)

C₄F₉SO₂NHCH₂CH₂OH (249 g, 0.725 mol; prepared according to U.S. Pat. No.7,169,323) and ClCH₂CH₂OCH₂CH₂OH (211 g, 1.70 mol) were batch charged toa 1000 mL, 3-necked round bottom flask equipped with a Claisen adapter,water cooled condenser, immersion thermocouple probe, mechanical stirrerand heating mantle. After heating mixture to a set point of 90° C.,potassium carbonate (120 g, 0.86 mol) was gradually added with stirringover a period of 15 minutes without significant exotherm or precipitate.Reaction temperature was increased to 120° C. and held for 17 hours.GC-FID analysis (in acetone) revealed the presence of about 37%unreacted ClCH₂CH₂OCH₂CH₂OH, no detectible C₄F₉SO₂NHCH₂CH₂OH, and 58.3%C₄F₉SO₂N(CH₂CH₂OCH₂CH₂OH)(CH₂CH₂OH). The batch temperature was loweredto 90° C. and 230 g of hot water was added. After addition of water 18 gof 85% phosphoric acid was added to the batch. The contents were phasesplit in a separatory funnel to give 385 g of lower fluorochemicalphase. The lower phase was returned to the flask and 100 ml of water,and 40 g of 86% phosphoric acid, were added and stirred with the batch.After sitting for an hour, no phase split could be seen. 377 g of methylt-butyl ether was added to the batch, which was allowed to stir for 15min. After the phase split, 759 g of methyl t-butyl ether productsolution was separated from 166 g of lower aqueous phase. The ethersolution was stripped at atmospheric pressure until the batchtemperature reached 77° C. The batch was further stripped at 8.6 mm Hguntil the pot temperature reached 132° C., and then the receiver wasemptied. Then stripping was continued until the pressure reached 2.2 mmHg at a head temperature of 171° C. The receiver was then emptied andcollection of the product cut was begun at 0.2 mm Hg vacuum and a headtemperature of 172° C. and a pot temperature of 184° C. Distillation wascontinued until the pot reached 195° C. to give 183 g of distillate.GC-FID analysis of the distillate showed the material to be 95.4%desired product (V). At room temperature the material crystallized to alow melting solid with a melting point of 45.1° C. as determined by DSC.

Synthesis 5: C₄F₉SO₂N(CH₃)(CH₂CH₂OCH₂CH₂OH), (VI)

C₄F₉SO₂NHCH₃ (339 g, 1.087 mol) (prepared as described in U.S. Pat. No.6,852,781) and ClCH₂CH₂OCH₂CH₂OH (314 g, 2.52 mol) were batch charged toa 2000 mL, 3-necked round bottom flask equipped with a Claisen adapter,water cooled condenser, immersion thermocouple probe, mechanical stirrerand heating mantle. After heating the mixture to a set point of 90° C.,potassium carbonate (179 g, 1.29 mol) was gradually added with stirringover a period of 15 minutes without significant exotherm or precipitate.Reaction temperature was increased to 120° C. and held for 17 hours.GC-FID analysis in acetone after overnight heating at 120° C. revealedthe presence of about 30% unreacted ClCH₂CH₂OCH₂CH₂OH, no detectibleC₄F₉SO₂NHCH₃, and 58.9% C₄F₉SO₂N(CH₃)(CH₂CH₂OCH₂CH₂OH). The batchtemperature was lowered to 90° C. and 300 g of hot water was added.After addition of water, 100 g of 85% phosphoric acid was added to thebatch. The contents were phase split in a separatory funnel to give 523g of lower fluorochemical phase. The bottom fluorochemical phase wasstripped at atmospheric pressure until the batch temperature reached140° C. The batch was further stripped at 63 mm Hg until the pottemperature reached 101° C., and then the receiver was emptied. Thenstripping was continued until the pressure reached 2.2 mm Hg and 152° C.The receiver was emptied and collection of the product cut was begun at0.2 mm Hg vacuum, at a head temperature of 125° C. and a pot temperatureof 149° C. Distillation was continued until the head temperature was132° C., and the pot temperature reached 152° C. to give 363 g ofmaterial. GC-FID analysis showed the material to be 97.8 area % thedesired product. C₄F₉SO₂N(CH₃)(CH₂CH₂OCH₂CH₂OH) was found to be a solidat room temperature with a melting point of 80.5° C. as determined byDSC. The chemical structure of this material was confirmed to be (VI) by¹H and ¹⁹F NMR analysis.

Synthesis 6: C₄F₉SO₂N(n-C₃H₇)(CH₂CH₂OCH₂CH₂OH), (VII)

C₄F₉SO₂NH(n-C₃H₇) (382 g, 1.137 mol) (prepared as described in U.S. Pat.No. 7,572,848) and ClCH₂CH₂OCH₂CH₂OH (328 g, 2.63 mol) were batchcharged to a 2000 mL, 3-necked round bottom flask equipped with aClaisen adapter, water cooled condenser, immersion thermocouple probe,mechanical stirrer and heating mantle. After heating mixture to a setpoint of 90° C., potassium carbonate (184 g, 1.33 mol) was graduallyadded with stirring over a period of 15 minutes without significantexotherm or precipitate. Reaction temperature was increased to 120° C.and held for 17 hours. GC analysis in acetone after overnight heating at120° C. revealed the presence of about 31% unreacted ClCH₂CH₂OCH₂CH₂OH,no detectible C₄F₉SO₂NH(n-C₃H₇), and 67.2 area %C₄F₉SO₂N(n-C₃H₇)(CH₂CH₂OCH₂CH₂OH). The batch temperature was lowered to90° C. and 380 g of hot water was added. After addition of water, 100 gof 85% phosphoric acid was added to the batch. The contents were phasesplit in a separatory funnel and the lower fluorochemical phase wasisolated. The fluorochemical phase was stripped at atmospheric pressureuntil the batch temperature reached 110° C. The batch was furtherstripped at 28 mm Hg until the pot temperature reached 140° C., and thenthe receiver was emptied. Distillation was continued at an initialpressure of 2.6 mm Hg until the head temperature reached 142° C., andthe pot temperature reached 164° C. and the pressure dropped to 0.6 mmHg to give 430 g of distillate. GC-FID analysis showed the collecteddistillate to be 100 area % desired product. The chemical structure ofthis material was confirmed to be (VII) by ¹H and ¹⁹F NMR analysis.

Synthesis 7: C₄F₉SO₂NH(CH₂CH₂OCH₂CH₂OCH₂CH₂OH) (VIII) andC₄F₉SO₂N(CH₂CH₂OCH₂CH₂OCH₂CH₂OH)₂ (IX)

C₄F₉SO₂NH₂ (640 g, 2.14 mol) and ClCH₂CH₂OCH₂CH₂OCH₂CH₂OH (288 g, 1.71mol, available from Aldrich, St. Louis, Mo.) were batch charged to a2000 mL, 3-necked round bottom flask equipped with a Claisen adapter,water cooled condenser, immersion thermocouple probe, mechanical stirrerand heating mantle. After heating mixture to a set point of 90° C.,sodium carbonate (189 g, 1.81 mol) was gradually added with stirringover a period of 15 minutes without significant exotherm or precipitate.Reaction temperature was increased to 120° C. and held for 17 hours. Thebatch temperature was lowered to 90° C. and 750 g of hot water was addedfollowed by 103 g of 85% phosphoric acid. The contents were phase splitin a separatory funnel. The lower fluorochemical phase was returned tothe flask and 508 ml of water, 53 g of 86% phosphoric acid, and 53 g ofsodium chloride were added and stirred with the batch, and then pouredback into a separatory funnel. The bottom layer was then phase split offto give 888 g of crude product. An aliquot of the washed crude wasremoved and analyzed by GC-FID in acetone revealing the presence ofabout 22% unreacted C₄F₉SO₂NH₂, 60% C₄F₉SO₂NH(CH₂CH₂OCH₂CH₂OCH₂CH₂OH)and 21% C₄F₉SO₂N(CH₂CH₂OCH₂CH₂OCH₂CH₂OH)₂. The crude product mixture wasstripped at atmospheric pressure until the pot temperature reached 150°C. The batch was then cooled to 90° C., and with good stirring thestripping was continued under vacuum to remove unreactedClCH₂CH₂OCH₂CH₂OCH₂CH₂OH and C₄F₉SO₂NH₂. Stripping was begun at 90° C.and 103 mm Hg to a receiver that was cooled in dry ice/acetone andcontinued until the pressure dropped to 0.4 mm Hg and the batch hadreached 100° C. The batch was cooled, vacuum was broken and the receiverwas emptied. The distillation was then continued at 0.4 mm Hg pressure.Cut 1 distilled at a head temp of 136-158° C. and a pot temp of 163-174°C. Cut 2 distilled at 0.2 mm Hg at a head temperature of 140-180° C. anda pot temperature of 174-195° C. and weighed 282 g. Cut 3 distilled at0.2 mm Hg at a head temperature of 181-193° C. and a pot temperature of193-215° C. and weighed 69 g. GC-FID analysis of Cut 2 revealed thepresence of 97.2% C₄F₉SO₂NH(CH₂CH₂OCH₂CH₂OCH₂CH₂OH) (VIII) and 2.8%C₄F₉SO₂N(CH₂CH₂OCH₂CH₂OCH₂CH₂OH)₂ (IX), and was a white solid at roomtemperature with a melting point of 58.5° C. GC-FID analysis of Cut 3revealed the presence of 66% C₄F₉SO₂NH(CH₂CH₂OCH₂CH₂OCH₂CH₂OH) (VIII)and 33.3% C₄F₉SO₂N(CH₂CH₂OCH₂CH₂OCH₂CH₂OH)₂ (IX). Cut 3 was a thickyellow liquid at room temperature. The chemical structure of the majorproduct collected in cut 2 was confirmed to be (VIII) by ¹H and ¹⁹F NMRanalysis.

Synthesis 8: C₄F₉SO₂N(CH₂CH₂OH)CH₂CH(CH₃)OH (X)

C₄F₉SO₂NHCH₂CH₂OH (500.00 g, 1.43 mol), K₂CO₃ powder (53 g, 0.39 mol),and anhydrous propylene carbonate (500 g, 4.9 mol) were batch charged toa 1.0 L round bottom 3-necked flask equipped with a Claisen adapter,water cooled condenser with nitrogen inlet line, immersion thermocoupleprobe, overhead stirrer and heating mantle. The reaction mixture wasgradually heated to 130° C. It was heated and stirred overnight. Aftercooling to 84° C., an aliquot of the reaction mixture was removed andanalyzed by GC in acetone. GC-FID analysis revealed the presence ofabout 56 area % unreacted propylene carbonate, 2.65% C₄F₉SO₂N(H)CH₂CH₂OHand 32.6% C₄F₉SO₂NCH₂CH₂OH [CH₂CH(CH₃)OH]. At 84° C., 800 ml of waterwas added to the batch followed by slow addition of 100 g of 85%phosphoric acid. The batch was phase split in a separatory funnel togive 884 g of lower crude fluorochemical product. The lower phase waswashed with 500 g of water with 10 g of NaCl dissolved in it to give 773g of lower fluorochemical layer. The fluorochemical phase was strippedat atmospheric pressure until the pot temperature reached 100° C.,giving 160 g of distillate. A precut was collected by distilling undervacuum (57 to 2 mm Hg) when the pot temperature was 35-143° C. A secondprecut was distilled at 2 to 1.4 mm Hg with a pot temperature of143-183° C. and a head temperature of 105-152° C., resulting in thecollection of 62 g of distillate. GC analysis of this second precut byGC-FID showed it to be 11.3 area H-FBSE and 72% the desired product (X).The main product cut was distilled at 1.4 to 0.2 mm Hg at a pot temp of183-215° C. and a head temperature of 150-160° C., yielding 308 g ofdistillate. GC analysis showed this material to be 70.6% desiredproduct. Recrystallization of the distilled main cut from toluene led tomaterial that was 98.4% desired product (X) by GC-FID.

Synthesis 9: C₂F₅SO₂N(CH₂CH₂OCH₂CH₂OH)₂, (E)

C₂F₅SO₂NH₂ (55.7 g, 0.279 mol; prepared according to the procedure forC₄F₉SO₂NH₂ as described in U.S. Pat. No. 7,169,323 with the exceptionthat C₄F₉SO₂F was replaced with C₂F₅SO₂F) and ClCH₂CH₂OCH₂CH₂OH (175 g,1.4 mol) were batch charged to a 1000 mL, 3-necked round bottom flaskequipped with a Claisen adapter, water cooled condenser, immersionthermocouple probe, mechanical stirrer and heating mantle. After heatingmixture to a set point of 90° C., potassium carbonate (113 g, 0.81 mol)was gradually added with stirring over a period of 15 minutes withoutsignificant exotherm or precipitate. Reaction temperature was increasedto 120° C. and held for 17 hours. The batch temperature was lowered to90° C. and 250 g of hot water and 33 g of 86% phosphoric acid wereadded. The contents were split in a separatory funnel to give 206 g oflower fluorochemical phase. GC-FID analysis of the lower fluorochemicalphase (in acetone) revealed the presence of 54.8% ClCH₂CH₂OCH₂CH₂OH plusC₂F₅SO₂NH₂ and 38.8% of the desired product (area %). The lowerfluorochemical phase was stripped at atmospheric pressure until the pottemperature reached 150° C. The batch was then cooled to 90° C., andwith good stirring the stripping was continued under vacuum to removeunreacted ClCH₂CH₂OCH₂CH₂OH and C₂F₅SO₂NH₂. Stripping was begun at 90°C. and 103 mm Hg to a receiver that was cooled in dry ice/acetone andcontinued until the vacuum was 2.5 mm Hg and the batch temperature hadreached 100° C. The batch was then cooled, vacuum was broken and thereceiver was emptied. The distillation was then continued at 2.5 mm Hg.Cut 1 distilled at a head temp of 146-148° C. and a pot temp of 189-206°C., and weighed 57 g. Cut 2 distilled at 0.2-2.0 mm Hg at a headtemperature of 159-180° C. and a pot temperature of 185-203° C. andweighed 13.3 g. GC-FID analysis of Cut 1 (in acetone) revealed it was93.6 area % desired product (E). Cut 2 was similarly analyzed and foundto be 89.8 area % desired product (E).

Surfactant Performance Testing Examples Examples 1-4: Solubility andSurface Tension of H-FBSP (I) with Ammonium Hydroxide

25% solutions of H-FBSP were prepared by dissolving molten H-FBSP inaqueous ammonium hydroxide (29% NH₃ in water available from KMGChemicals, Houston, Tex.) which had been diluted with 18.2 megaohm DIwater. The mole ratio—defined as the moles of base to the moles offluorochemical surfactant—was varied. The solutions were mixed for onehour and allowed to settle over night. Examples were prepared asdescribed in Table 3.

TABLE 3 Sample Preparation of H-FBSP in Aqueous NH₄OH Mass Mass 29% MassMole Water NH₃ H-FBSP Example Ratio (g) (g) (g) Soluble 1 2.0 3.3570.396 1.256 Yes 2 1.5 3.443 0.299 1.250 Yes 3 1.0 3.552 0.208 1.249 No 40.5 3.649 0.109 1.249 No

The homogeneous solutions were diluted in water for surface tension andsolubility measurements. Surface tension and solubility results aresummarized in Table 4.

TABLE 4 H-FBSP in Aqueous NH₄OH Diluted in Water Concentration SurfaceTension Sample (ppm) (dyn/cm) Soluble Example 1 2000 51.6 Yes Mole Ratio2.0 4000 46.2 Yes 6000 42.8 Yes 8000 40.5 Yes Example 2 2000 47.9 YesMole Ratio 1.5 4000 41.6 Yes 6000 37.9 Yes 8000 35.6 Yes

Examples 5-8: Solubility and Surface Tension of H-FBS(EE) (III) withAmmonium Hydroxide

25% solutions of H-FBS(EE) were prepared by dissolving the H-FBS(EE)liquid in aqueous ammonium hydroxide which had been diluted with 18.2megaohm water. The solutions were mixed for one hour and allowed tosettle over night. Examples were prepared as described in Table 5.

TABLE 5 Sample Preparation of H-FBS(EE) in Aqueous NH₄OH Mass Mass 29%Mass Mole Water NH₃ H-FBS(EE) Example Ratio (g) (g) (g) Soluble 5 2.02.692 0.305 0.998 Yes 6 1.5 2.773 0.231 0.999 Yes 7 1.0 2.854 0.1530.992 Yes 8 0.5 2.915 0.077 0.993 Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 6.

TABLE 6 H-FBS(EE) in Aqueous NH₄OH Diluted in Water ConcentrationSurface Tension Sample (ppm) (dyn/cm) Soluble Example 5 1000 47.9 YesMole Ratio 2.0 2000 42.1 Yes 4000 35.5 Yes 6000 32.9 Yes 8000 30.4 YesExample 6 1000 46.6 Yes Mole Ratio 1.5 2000 41.1 Yes 4000 34.5 Yes 600031.4 Yes 8000 28.8 Yes Example 7 1000 36.8 Yes Mole Ratio 1.0 2000 30.3Yes 4000 24.1 Yes 6000 21.1 Yes 8000 20.1 Yes Example 8 1000 29.4 YesMole Ratio 0.5 2000 24.7 2^(nd) Liquid Phase 4000 21.0 2^(nd) LiquidPhase

Examples 9-12: Solubility and Surface Tension of H-FBS(EE) (III) withTetramethyl Ammonium Hydroxide

25% solutions of H-FBS(EE) were prepared by dissolving the H-FBS(EE)liquid in aqueous tetramethylammonium hydroxide (TMAH, 25% TMAH in wateravailable from Alfa Aesar, Ward Hill, Mass.) which had been diluted with18.2 megaohm water. The solutions were mixed for one hour and allowed tosettle over night. Examples were prepared as described in Table 7.

TABLE 7 Sample Preparation of H-FBS(EE) in Aqueous TMAH Mass Mass 25%Mass Mole Water TMAH H-FBS(EE) Example Ratio (g) (g) (g) Soluble 9 2.01.401 2.351 1.258 Yes 10 1.5 1.989 1.761 1.248 Yes 11 1.0 2.573 1.1831.248 Yes 12 0.5 3.153 0.597 1.260 Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 8.

TABLE 8 H-FBS(EE) in Aqueous TMAH Diluted in Water Concentration SurfaceTension Sample (ppm) (dyn/cm) Soluble Example 9 1000 46.4 Yes Mole Ratio2.0 2000 41.4 Yes 4000 35.8 Yes 6000 32.4 Yes 8000 30.3 Yes Example 101000 46.5 Yes Mole Ratio 1.5 2000 41.0 Yes 4000 35.7 Yes 6000 32.5 Yes8000 30.0 Yes Example 11 1000 45.4 Yes Mole Ratio 1.0 2000 40.6 Yes 400034.7 Yes 6000 32.4 Yes 8000 29.5 Yes Example 12 1000 28.2 Yes Mole Ratio0.5 1500 24.1 No 2000 23.4 No 4000 20.3 No

Examples 13-16: Solubility and Surface Tension of H-FBS(EEE) (VIII) withAmmonium Hydroxide

25% solutions of H-FBS(EEE) were prepared by dissolving moltenH-FBS(EEE) in aqueous ammonium hydroxide which had been diluted with18.2 megaohm water. The solutions were mixed for one hour and allowed tosettle over night. Examples were prepared as described in Table 9.

TABLE 9 Sample Preparation of H-FBS(EEE) in Aqueous NH₄OH Mass Mass 29%Mass Mole Water NH₃ H-FBS(EEE) Example Ratio (g) (g) (g) Soluble 13 2.06.795 0.696 2.503 Yes 14 1.5 6.972 0.533 2.513 Yes 15 1.0 7.151 0.3472.502 Yes 16 0.5 7.325 0.178 2.498 Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 10.

TABLE 10 H-FBS(EEE) in Aqueous NH₄OH Diluted in Water ConcentrationSurface Tension Sample (ppm) (dyn/cm) Soluble Example 13 1000 39.9 YesMole Ratio 2.0 2000 35.2 Yes 4000 31.4 Yes 6000 29.2 Yes 8000 27.6 YesExample 14 1000 38.7 Yes Mole Ratio 1.5 2000 33.3 Yes 4000 29.4 Yes 600026.6 Yes 8000 25.4 Yes Example 15 1000 34.0 Yes Mole Ratio 1.0 2000 28.4Yes 4000 24.5 Yes 6000 22.5 Yes 8000 20.8 Yes Example 16 1000 26.5 YesMole Ratio 0.5 1500 23.8 Yes 2000 23.2 Yes 3000 21.2 No 4000 21.6 No

Examples 17 & 18: Solubility and Surface Tension of H-FBSP (I) Blends inAmmonium Hydroxide

Blends of 22% H-FBSP and 3% of a neutral surfactant were made bydissolving molten H-FBSP with the following neutral surfactants—FBSEE(B; prepared as described in U.S. Patent Application Pub. No.2010/0160458) or FBSPP (II), in aqueous ammonium hydroxide which hadbeen diluted in 18.2 megaohm water. The solutions were mixed for onehour and allowed to settle over night. Examples were prepared asdescribed in Table 11.

TABLE 11 Sample Preparation of H-FBSP + Neutral Surfactants in AqueousNH₄OH Example 17 18 Neutral FBSEE FBSPP Mass Water (g) 3.348 3.351 Mass29% NH₃ (g) 0.397 0.399 Mass H-FBSP (g) 1.103 1.102 Mass Neutral (g)0.154 0.151 Soluble Yes Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in the Table 12.

TABLE 12 H-FBSP + Neutral Surfactants in Aqueous NH₄OH Diluted in WaterConcentration Surface Tension Sample (ppm) (dyn/cm) Soluble Example 172000 30.5 Yes FBSEE Example 18 500 35.4 Yes FBSPP 1000 31.2 LightPrecipitate 2000 26.6 Precipitate

Examples 19-23: Solubility and Surface Tension of H-FBS(EE) (III) Blendsin Ammonium Hydroxide

Blends of 22% H-FBS(EE) and 3% of a neutral surfactant were made bydissolving H-FBS(EE) with each of the following neutral surfactants—FBSEE (B; prepared as described in U.S. Patent Application Pub. No.2010/0160458), FBS(EE)2 (IV), FBSPE (X), FBSE(EE) (V) or Pr-FBS(EE)(VII). Solutions were prepared in aqueous ammonium hydroxide which hadbeen diluted in 18.2 megaohm water. The solutions were mixed for onehour and allowed to settle over night. Examples were prepared asdescribed in Table 13.

TABLE 13 Sample Preparation of H-FBS(EE) + Neutral Surfactants inAqueous NH₄OH Example 19 20 21 22 23 Neutral FBSEE FBS(EE)2 FBSPE Me-Pr- FBS(EE) FBS(EE) Mass Water (g) 2.699 2.699 6.734 6.748 2.696 Mass29% NH₃ 0.296 0.296 0.764 0.752 0.306 (g) Mass H-FBS(EE) 0.886 0.8802.204 2.212 0.883 (g) Mass Neutral (g) 0.116 0.119 0.301 0.303 0.117Soluble Yes Yes Yes Yes Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 14.

TABLE 14 H-FBS(EE) + Neutral Surfactants in Aqueous NH₄OH Diluted inWater Concentration Surface Tension Sample (ppm) (dyn/cm) SolubleExample 19 1000 36.5 Yes FBSEE 2000 29.3 Yes 4000 22.4 Yes Example 201000 34.1 Yes FBS(EE)2 2000 22.4 Yes 4000 22.8 Yes Example 21 1000 20.8Yes FBSPE 2000 19.4 Yes 4000 18.9 Yes 6000 18.3 No Example 22 1000 27.1Yes FBSE(EE) 2000 23.7 Yes 4000 19.9 Yes 6000 18.9 Yes 8000 18.9 YesExample 23 1000 23.2 Yes Pr-FBS(EE) 2000 22.7 No 4000 21.8 No

Examples 24-26: Solubility and Surface Tension of H-FBS(EEE) (VIII)Blends in Ammonium Hydroxide

Blends of 22% H-FBS(EEE) and 3% of a neutral surfactant were made bydissolving H-FBS(EEE) with each of the following neutral surfactants—FBSEE (B), FBS(EE)2 (IV) or FBS(EEE)2 (IX). The FBS(EEE)2 usedconsisted of 33% FBS(EEE)2 and 66% H-FBS(EEE). Blend ratios wereadjusted to account for this. Solutions were prepared in aqueousammonium hydroxide which had been diluted in 18.2 megaohm water. Thesolutions were mixed for one hour and allowed to settle over night.Examples were prepared as described in Table 15.

TABLE 15 Sample Preparation of H-FBS(EEE) + Neutral Surfactants inAqueous NH₄OH Example 24 25 26 Neutral FBSEE FBS(EE)2 FBS(EEE)2 MassWater (g) 6.798 3.407 3.403 Mass 29% NH3 (g) 0.701 0.355 0.357 MassH-FBS(EEE) (g) 2.198 1.101 0.782 Mass Neutral (g) 0.300 0.150 0.450Soluble Yes Yes Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 16.

TABLE 16 H-FBS(EEE) + Neutral Surfactants in Aqueous NH₄OH Diluted inWater Concentration Surface Tension Sample (ppm) (dyn/cm) SolubleExample 24 1000 35.1 Yes FBSEE 2000 28.6 Yes 4000 20.8 Yes 6000 19.2 No8000 19.6 No Example 25 1000 31.6 Yes FBS(EE)2 2000 24.5 Yes 4000 21.0Yes 6000 20.5 Yes 8000 21.2 Yes Example 26 1000 31.2 Yes FBS(EEE)2 200026.0 Yes 4000 22.2 Yes 6000 22.1 Yes 8000 23.1 Yes

Examples 27-31: Solubility and Surface Tension of H-FBSE (A) Blends inAmmonium Hydroxide

Blends of 22% H-FBSE and 3% of a neutral surfactant were made bydissolving H-FBSE with each of the following neutral surfactants—FBS(EE)2 (IV), FBSE(EE) (V), FBSPE (X), Me-FBS(EE) (VI) or Pr-FBS(EE)(VII). Solutions were prepared in aqueous ammonium hydroxide which hadbeen diluted in 18.2 megaohm water. The solutions were mixed for onehour and allowed to settle over night. Examples were prepared asdescribed in Table 17.

TABLE 17 Sample Preparation of H-FBSE + Neutral Surfactants in AqueousNH₄OH Example 27 28 29 30 31 Neutral FBS(EE)2 FBSE(EE) FBSPE Me- Pr-FBS(EE) FBS(EE) Mass Water (g) 6.65 6.647 6.649 6.662 6.661 Mass 29% NH₃0.85 0.864 0.846 0.848 0.856 (g) Mass H-FBSE 2.20 2.201 2.203 2.19 2.21  (g) Mass Neutral 0.30 0.300 0.296 0.30  0.300 (g) Soluble Yes YesYes Yes Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 18.

TABLE 18 H-FBSE + Neutral Surfactants in Aqueous NH₄OH Diluted in WaterConcentration Surface Tension Sample (ppm) (dyn/cm) Soluble Example 272000 21.6 Yes FBS(EE)2 4000 19.6 Yes 6000 20.0 Yes 8000 20.6 Yes Example28 500 24.2 Yes FBSE(EE) 1000 23.7 Yes 2000 23.5 Yes 4000 20.6 Yes 600018.6 Yes 8000 18.3 Yes Example 29 1000 24.5 Yes FBSPE 2000 20.4 Yes 400019.2 Yes 5000 18.5 Yes 6000 18.3 Very light haze Example 30 1000 26.1Yes Me-FBS(EE) 2000 17.6 Yes 2200 18.1 Yes 2500 17.6 No Example 31 100023.7 Yes Pr-FBS(EE) 2000 23.6 No 4000 23.5 No

Example 32: Solubility and Surface Tension of FBSE(EE) (V)

A 1% solution of FBSE(EE) was prepared by dissolving molten FBSE(EE) in18.2 megaohm water. The solution was mixed for one hour and allowed tosettle over night. Example 32 was prepared as described in Table 19.

TABLE 19 Sample Preparation of FBSE(EE) in Water Mass Water MassFBSE(EE) Example (g) (g) Soluble 32 9.903 0.102 Yes

The solution was diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 20.

TABLE 20 FBSE(EE) Diluted in Water Concentration Surface Tension Sample(ppm) (dyn/cm) Soluble Example 32 25 48.2 Yes 50 41.1 Yes 100 32.2 Yes250 27.4 Yes 500 21.6 Yes 1000 18.4 Yes

Example 33: Solubility and Surface Tension of Pr-FBS(EE) (VII)

A 1% solution of Pr-FBS(EE) was prepared by dissolving molten Pr-FBS(EE)in iso-propyl alcohol (IPA, available from Honeywell, Morristown, N.J.).The solution was mixed and allowed to settle. Example 33 was prepared asdescribed in Table 21.

TABLE 21 Sample Preparation of Pr-FBS(EE) in IPA Mass IPA MassPr-FBS(EE) Example (g) (g) Soluble 33 10.890 0.110 Yes

The solution was diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 22.

TABLE 22 Pr-FBS(EE) Diluted in Water Concentration Surface TensionSample (ppm) (dyn/cm) Soluble Example 33 25 32.7 Yes 50 27.1 Yes 10023.7 Yes 125 23.6 Yes 150 23.2 Yes

Example 34: Solubility and Surface Tension of FBS(EE)2 (IV)

FBS(EE)2 was diluted in water for surface tension and solubilitymeasurements (Example 34). The results for example 34 are summarized inTable 23.

TABLE 23 FBS(EE)2 Diluted in Water Concentration Surface Tension Sample(ppm) (dyn/cm) Soluble Example 34 50 41.8 Yes 100 35.9 Yes 250 27.6 Yes500 22.6 Yes

Comparative Examples 1-4—Solubility and Surface Tension of H-FBSE (A)with Ammonium Hydroxide

25% solutions of H-FBSE were prepared by dissolving molten H-FBSE inaqueous ammonium hydroxide which had been diluted with 18.2 megaohmwater. The solutions were mixed for one hour and allowed to settle overnight. Comparative examples 1 to 4 were prepared as described in Table24.

TABLE 24 Sample Preparation of H-FBSE in Aqueous NH₄OH Comparative MassMass Example Mole Mass Water 29% NH₃ H-FBSE (CE) Ratio (g) (g) (g)Soluble CE 1 2.0 6.65 0.85 2.49 Yes CE 2 1.5 6.85 0.63 2.51 Yes CE 3 1.07.07 0.45 2.50 Yes CE 4 0.5 7.29 0.22 2.51 Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 25.

TABLE 25 H-FBSE in Aqueous NH₄OH Diluted in Water Concentration SurfaceTension Sample (ppm) (dyn/cm) Soluble CE 1 1000 60.7 Yes Mole Ratio 2.02000 50.2 Yes 4000 49.2 Yes 6000 42.8 Yes 8000 41.2 Yes CE 2 1000 49.5Yes Mole Ratio 1.5 2000 45.9 Yes 4000 40.1 Yes 6000 37.4 Yes 8000 35.5Yes CE 3 1000 41.7 Yes Mole Ratio 1.0 2000 34.5 Yes 4000 27.9 Yes 600023.6 Yes 8000 20.8 Yes CE 4 1000 29.9 Yes Mole Ratio 0.5 2000 22.7 Yes3000 18.4 No 4000 17.8 No

Comparative Example 5: Solubility and Surface Tension of Blend of H-FBSE(A) and FBSEE (B) with Ammonium Hydroxide

A 25% solution of a blend of H-FBSE and FBSEE were prepared bydissolving the molten H-FBSE and FBSEE in aqueous ammonium hydroxidewhich had been diluted with 18.2 megaohm water. The solution was mixedfor one hour and allowed to settle over night. Comparative example 5 wasprepared as described in Table 26.

TABLE 26 Sample Preparation of H-FBSE + FBSEE in Aqueous NH₄OH Mass MassMass Comparative Mass Water 29% NH₃ H-FBSE FBSEE Example (g) (g) (g) (g)Soluble CE 5 6.65 0.85 2.20 0.30 Yes

The solution was diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 27.

TABLE 27 H-FBSE + FBSEE in Aqueous NH₄OH Diluted in Water ConcentrationSurface Tension Sample (ppm) (dyn/cm) Soluble CE 5 2000 31.3 Yes 400024.3 Yes 6000 24.5 No

Comparative Examples 6-7: Solubility and Surface Tension of Blend ofFES(EE)2 (E) with H-FBS(EE) (III) and H-FBS(EEE) (VIII) in AqueousAmmonium Hydroxide

A 25% blend of FES(EE)2 with H-FBS(EE) was prepared by dissolvingH-FBS(EE) and FES(EE)2 in aqueous ammonium hydroxide which had beendiluted in 18.2 megaohm water. A similar solution was prepared usingFES(EE)2 and H-FBS(EEE). The solutions were mixed for one hour andallowed to settle overnight. Comparative examples 6 and 7 were preparedas described in Table 28.

TABLE 28 Sample Preparation of FES(EE)2 with Anionic Surfactants inAqueous NH₄OH Comparative Example CE 6 CE 7 Anionic H-FBS(EE) H-FBS(EEE)Mass Water (g) 3.371 3.396 Mass 29% NH₃ (g) 0.386 0.349 Mass Anionic (g)1.096 1.101 Mass FES(EE)2 0.150 0.154 Soluble Yes Yes

The solutions were diluted in water for surface tension and solubilitymeasurements. The results are summarized in Table 29.

TABLE 29 FES(EE)2 + Anionic Surfactants in Aqueous NH₄OH Diluted inWater Comparative Surface Example Concentration Tension Soluble CE 61000 45.2 Yes H-FBS(EE) + 2000 39.5 Yes FES(EE)2 4000 33.9 Yes 6000 30.7Yes 8000 28.2 Yes CE 7 1000 42.5 Yes H-FBS(EEE) + 2000 35.6 Yes FES(EE)24000 29.8 Yes 6000 27.8 Yes 8000 26.4 YesComparison of Water Contact Angles after Rinsing

The shift in the contact angle of water on a photoresist after exposureto a surfactant solution was measured using a DSA 100 (available fromKrüss of Hamburg, Germany).

A photoresist material (EPIC 2135 193 nm photoresist available from DowChemical Co., Midland, Mich.) was spin coated on one side of a piece ofsilicon wafer—approximately 1 inch by 1 inch using a spin rate of 1500rpm for 27 seconds. The photoresist was baked to drive off solvent byplacing the wafer on a hot plate at 120° C. for 60 seconds.

The wafer coated with resist was placed in a spin coater (WS-650MZ-23NPP/LITE from Laurell Technologies of North Wales, Pa.) with amodified chuck. While the wafer was spinning at 300 rpm, 1 mL of 2.38%TMAH (available from Alfa Aesar of Ward Hill, Mass.) was applied to thewafer over 20 seconds. This was followed by 10 mL of 18.2 megaohm waterapplied over 60 seconds and then 1.5 mL of surfactant solution appliedover 40 seconds. The spin rate was then increased to 1500 rpm and heldfor 15 seconds. While still spinning at 1500 rpm, a nitrogen stream wasthen placed over the wafer for 15 seconds. The water contact angle wasthen immediately measured.

The measured static water contact angles are reported in Table 30. Allthe surfactant solutions in the table were diluted to 2000 ppm totalsurfactant in water. In all cases, there were no visible changes to thephotoresist after exposure to the surfactant solution.

TABLE 30 Static Water Contact Angle on Photoresist Water Example SampleContact Angle N/A Wafer - No Resist 34.1 (±0.8) N/A Resist - No Rinse64.7 (±1.3) N/A Resist - TMAH + Water Only 56.6 (±1.0) ComparativeExample 5 H-FBSE/FBSEE 41.0 (±0.6) Example 27 H-FBSE/FBS(EE)2 44.3(±1.0) Example 28 H-FBSE/FBSE(EE) 45.7 (±0.9) Example 24H-FBS(EEE)/FBSEE 43.2 (±0.6) Example 25 H-FBS(EEE)/FBS(EE)2 42.4 (±1.3)Example 26 H-FBS(EEE)/FBS(EEE)2 39.6 (±0.8) Comparative Example 1H-FBSE, Mole Ratio 2.0 54.7 (±1.7) Comparative Example 3 H-FBSE, MoleRatio 1.0 49.1 (±1.9) Example 5 H-FBS(EE), Mole Ratio 2.0 46.4 (±0.6)Example 7 H-FBS(EE), Mole Ratio 1.0 45.8 (±0.6) Example 13 H-FBS(EEE),Mole Ratio 2.0 43.9 (±1.1) Example 15 H-FBS(EEE), Mole Ratio 1.0 44.5(±0.8)

The results of these experiments demonstrate that the choice ofsurfactants, blending of selected anionic and neutral surfactants, andadjusting pH can affect water contact angles on developed and rinsedphotoresist surface, thus providing a means to control contact angles.

Comparison of Surfactant Absorption on Photoresist

The absorption of several surfactant solutions diluted in water to aphotoresist material (EPIC 2135 193 nm photoresist) was measured using aQ-Sense E4 QCM-D microbalance (available from Biolin Scientific, VästraFrölunda, SWEDEN). This instrument analyzes both the dissipation andfrequency shift of a quartz crystal sensor to characterize thin filmscoated on the sensor. This allows the mass of material absorbed and theviscoelastic properties of the thin film to be measured. In theseparticular experiments, it allows measurement of the mass of surfactantabsorbed onto or into the photoresist material during exposure of theresist to the surfactant solution.

A gold plated quartz crystal sensor (QSX 301, Biolin Scientific, Sweden)was single side coated with photoresist (EPIC 2135 193 nm) by spincoating. One to three droplets of the resist material were applied to aclean sensor. The sensor was then spun at 1500 rpm for 27 seconds. Theresist was baked to drive off solvent by placing the sensor on a hotplate at 120° C. for 60 seconds.

The coated sensors were then tested in three stages. During all stages,dissipation and frequency shift were monitored on multiple bands. In thefirst phase, 18 megaohm water was run over the sensor (at 150 μL/min)for five minutes to establish a baseline. No frequency shift ordissipation was observed during this stage. Once the baseline wasestablished, the second stage was started by switching the flow to thesurfactant solution (at 150 μL/min). This flow was continued until thefrequency shift and dissipation stabilized (generally 15 minutes).Reported values for frequency shift were measured at this time. In thethird stage, the flow was switched back to pure 18 megaohm water (at 150μL/min). The shift in frequency and dissipation were again monitored for10 minutes to determine if surfactant absorption was reversible.

The steady state frequency shifts due to absorption of severalsurfactants from solution at 2000 ppm in water during surfactantsolution flow are recorded in Table 31 below.

TABLE 31 Absorption Values by QCM-D on Photoresist AbsorptionSet/Example Sample (ΔV′) Comparative Example 5 H-FBSE/FBSEE 4.0 Example27 H-FBSE/FBS(EE)2 8.2 Example 28 H-FBSE/FBSE(EE) 9.9 Example 24H-FBS(EEE)/FBSEE 6.7 Example 25 H-FBS(EEE)/FBS(EE)2 7.9 Example 26H-FBS(EEE)/FBS(EEE)2 7.5 Comparative Example 1 H-FBSE, Mole Ratio 2.02.0 Comparative Example 3 H-FBSE, Mole Ratio 1.0 3.8 Example 5H-FBS(EE), Mole Ratio 2.0 3.1 Example 7 H-FBS(EE), Mole Ratio 1.0 5.7Example 13 H-FBS(EEE), Mole Ratio 2.0 4.0 Example 15 H-FBS(EEE), MoleRatio 1.0 6.7

The results of these experiments demonstrate that the choice ofsurfactants, blending of selected anionic and neutral surfactants, andadjusting pH can affect the level (or mass) of surfactant absorbed ontoor into the photoresist from aqueous rinse solutions, thus providing ameans to control surfactant absorption by the photoresist. This in turncan provide control of contact angles on the resist surface as well asvarious lithography performance attributes such as defectivity (numbersof watermarks and particle defects), line melting, line width roughness,line edge roughness and process windows.

Comparisons of Surface Tension Performance and Solubility: Comparison ofH-FBSE, H-FBSP, H-FBS(EE) and H-FBS(EEE) in Aqueous Ammonium Hydroxide

Surface tension and solubility results in water from examples 1, 5, 13and comparative example 1 are summarized in Table 32 below for moleratio of 2.0.

TABLE 32 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous Ammonia, MR2.0 Concentration H-FBSP H-FBS(EE) H-FBS(EEE) H-FBSE(ppm) (Ex 1) (Ex 5) (Ex 13) (CE 1) 1000 47.9/Yes 39.9/Yes 60.7/Yes 200051.6/Yes 42.1/Yes 35.2/Yes 50.2/Yes 4000 46.2/Yes 35.5/Yes 31.4/Yes49.2/Yes 6000 42.8/Yes 32.9/Yes 29.2/Yes 42.8/Yes 8000 40.5/Yes 30.4/Yes27.6/Yes 41.2/Yes

All solutions tested were soluble. The H-FBS(EE) and H-FBS(EEE) providelower surface tension in water than the H-FBSE at the sameconcentrations with the H-FBS(EEE) providing the lowest surface tensionin water of all the materials tested. H-FBSE and H-FBSP provide roughlyequivalent surface tensions.

Surface tension and solubility results in water from examples 2, 6, 14and comparative example 2 are summarized in Table 33 below for moleratio of 1.5.

TABLE 33 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous Ammonia, MR1.5 Concentration H-FBSP H-FBS(EE) H-FBS(EEE) H-FBSE(ppm) (Ex 2) (Ex 6) (Ex 14) (CE 2) 1000 46.6/Yes 38.7/Yes 49.5/Yes 200047.9/Yes 41.1/Yes 33.3/Yes 45.9/Yes 4000 41.6/Yes 34.5/Yes 29.4/Yes40.1/Yes 6000 37.9/Yes 31.4/Yes 26.6/Yes 37.4/Yes 8000 35.6/Yes 28.8/Yes25.4/Yes 35.5/Yes

The relative performance of these surfactants for the mole ratio of 1.5follows the same trend as the mole ratio of 2.0, above.

Surface tension and solubility results in water from examples 3, 7, 15and comparative example 3 are summarized in Table 34 below for moleratio of 1.0.

TABLE 34 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous Ammonia, MR1.0 Concentration H-FBSP H-FBS(EE) H-FBS(EEE) H-FBSE(ppm) (Ex 3) (Ex 7) (Ex 15) (CE 3) 1000 Concentrate is 36.8/Yes 34.0/Yes41.7/Yes 2000 not soluble 30.3/Yes 28.4/Yes 34.5/Yes 4000 24.1/Yes24.5/Yes 27.9/Yes 6000 21.1/Yes 22.5/Yes 23.6/Yes 8000 20.1/Yes 20.8/Yes20.8/Yes

All the tested dilutions in water are soluble. H-FBS(EE) and H-FBS(EEE)provide lower surface tensions than H-FBSE at low surfactantconcentrations in water. At higher surfactant concentrations, thesurface tension results are equivalent for all three.

Surface tension and solubility results in water from examples 4, 8, 16and comparative example 4 are summarized in Table 35 below for moleratio of 0.5.

TABLE 35 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous Ammonia, MR0.5 Concentration H-FBSP H-FBS(EE) H-FBS(EEE) H-FBSE(ppm) (Ex 4) (Ex 8) (Ex 16) (CE 4) 1000 Concentrate is 29.4/Yes 26.5/Yes29.9/Yes 2000 not soluble 24.7/No 23.2/Yes 22.7/Yes 4000 21.0/No 21.6/No17.8/No

All of the anionic surfactants tested have limited solubility underthese conditions. In the soluble range, the surface tensions are similarfor all three materials.

Comparison of H-FBSE, H-FBS(EE) and H-FBS(EEE) in Aqueous TMAH

Surface tension and solubility results in water from Example 9(H-FBS(EE)) and similar data collected for H-FBS(EEE) and H-FBSE underidentical conditions are summarized in Table 36 below for a mole ratioof 2.0.

TABLE 36 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous TMAH, MR2.0 Concentration H-FBS(EE) H-FBS(EEE) H-FBSE (ppm) (Ex9) (Ex 35) (CE 8) 1000 46.4/Yes 47.3/Yes 62.3/Yes 2000 41.4/Yes 42.6/Yes59.0/Yes 4000 35.8/Yes 38.6/Yes 55.3/Yes 6000 32.4/Yes 35.0/Yes 51.3/Yes8000 30.3/Yes 32.8/Yes 49.3/Yes

All solutions tested were completely soluble. The H-FBS(EE) andH-FBS(EEE) surfactants provide significantly lower surface tension inwater than H-FBSE at the same concentrations.

Surface tension and solubility results in water from Example 10(H-FBS(EE)) and similar data collected for H-FBS(EEE) and H-FBSE underidentical conditions are summarized in Table 37, below, for a mole ratioof 1.5.

TABLE 37 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous TMAH, MR1.5 Concentration H-FBS(EE) H-FBS(EEE) H-FBSE (ppm) (Ex10) (Ex 36) (CE 9) 1000 46.5/Yes 47.4/Yes 60.8/Yes 2000 41.0/Yes42.9/Yes 61.3/Yes 4000 35.7/Yes 37.9/Yes 55.0/Yes 6000 32.5/Yes 35.7/Yes52.7/Yes 8000 30.0/Yes 33.5/Yes 49.9/Yes

Relative surface tension and solubility results are similar to the MR2.0 results, described above.

Surface tension and solubility results in water from Example 11(H-FBS(EE)) and similar data collected for H-FBS(EEE) and H-FBSE underidentical conditions are summarized in Table 38 below for a mole ratioof 1.0.

TABLE 38 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous TMAH, MR1.0 Concentration H-FBS(EE) H-FBS(EEE) H-FBSE (ppm) (Ex11) (Ex 37) (CE 10) 1000 45.4/Yes 44.2/Yes 53.3/Yes 2000 40.6/Yes42.2/Yes 47.1/Yes 4000 34.7/Yes 36.6/Yes 46.6/Yes 6000 32.4/Yes 33.2/Yes42.9/Yes 8000 29.5/Yes 30.3/Yes 42.5/Yes

Both H-FBS(EE) and H-FBS(EEE) provide significantly lower surfacetensions than H-FBSE at equivalent concentrations when tested at thismole ratio (MR1.0), similar to results at higher MR.

Surface tension and solubility results in water from Example 12(H-FBS(EE)) and similar data collected for H-FBS(EEE) and H-FBSE underidentical conditions are summarized in Table 39, below, for a mole ratioof 0.5.

TABLE 39 Surface Tension (dyn/cm)/Solubility of Anionic Surfactants inAqueous TMAH, MR0.5 Concentration H-FBS(EE) H-FBS(EEE) H-FBSE (ppm) (Ex12) (Ex 38) (CE 11) 1000 28.2/Yes 26.7/Yes 31.1/Yes 2000 23.4/No22.8/Yes 24.1/Yes 4000 20.3/No 20.8/No 16.7/No

All of the anionic surfactants tested have limited solubility underthese conditions. In the soluble range, the surface tensions ofH-FBS(EE) and H-FBS(EEE) are slightly lower than those provided byH-FBSE.

Comparison of FBSEE, FBS(EE)2 and FBSE(EE) Blended with H-FBSE inAqueous Ammonium Hydroxide

Surface tension and solubility results in water from examples 27, 28 andcomparative example 5 are summarized in Table 40. For the data presentedbelow, the concentrates were prepared at 22 wt % H-FBSE and 3 wt % ofeither FBSEE, FBS(EE)2, or FBSE(EE) in aqueous ammonium hydroxide, andthen diluted with water to the stated concentration.

TABLE 40 Surface Tension (dyn/cm)/Solubility of Neutral SurfactantBlends with H-FBSE Concentration FBSE(EE) FBS(EE)2 FBSEE (ppm) (Ex 28)(Ex 27) (CE 5) 2000 23.5/Yes 21.6/Yes 31.3/Yes 4000 20.6/Yes 19.6/Yes24.3/Yes 6000 18.6/Yes 20.0/Yes 24.5/No 8000 18.3/Yes 20.6/Yes

Blends of FBSE(EE) and FBS(EE)2 with H-FBSE provide lower surfacetension and better solubility than the comparative H-FBSE/FBSEE blend.

Comparison of Blends of FBSEE, FBS(EE)2 and FBS(EEE)2 with H-FBS(EEE) inAqueous Ammonium Hydroxide Vs. FBSEE/H-FBSE Blend

Surface tension and solubility results in water for surfactantsdescribed Examples 24-26 are summarized in Table 41 below. Theconcentrates for these examples were prepared at 22 wt % H-FBS(EEE)blended with 3 wt % of either FBSEE, FBS(EE)2, or FBS(EEE)2 in aqueousammonium hydroxide, and then diluted with water to the statedconcentration. Comparative results for the blend of H-FBSE/FBSEEprepared and tested under identical conditions (Comparative Example 5)are included for comparison.

TABLE 41 Surface Tension (dyn/cm)/Solubility of Neutral SurfactantBlends with H-FBS(EEE) Concentration FBS(EE)2 FBS(EEE)2 FBSEEH-FBSE/FBSEE (ppm) (Ex 25) (Ex 26) (Ex 24) (CE 5) 1000 31.6/Yes 31.2/Yes35.1/Yes — 2000 24.5/Yes 26.0/Yes 28.6/Yes 31.3/Yes 4000 21.0/Yes22.2/Yes 20.8/Yes 24.3/Yes 6000 20.5/Yes 22.1/Yes 19.2/No 24.5/No 800021.2/Yes 23.1/Yes 19.6/No —

Measured surface tensions are slightly lower for blends of FBS(EE)2 andFBS(EEE)2 with H-FBS(EEE) than the H-FBS(EEE)/FBSEE blend at lowconcentrations (1000-2000 ppm). In addition, the H-FBS(EEE) blends withFBS(EE)2 and FBS(EEE)2 provide higher solubility in water than theH-FBS(EEE)/FBSEE blend or the comparative H-FBSE/FBSEE blend. All of thesurfactant blends of the present invention tested here, comprising atleast one surfactant component having at least one oligomeric ethyleneoxide group, provide lower surface tensions than the comparative blendof H-FBSE/FBSEE when prepared and tested under identical conditions inaqueous ammonium hydroxide.

Comparison of Blends of FES(EE)2 and FBS(EE)2 with H-FBS(EEE) in AqueousAmmonium Hydroxide

Surface tension and solubility results in water for the surfactantsdescribed in example 25), Comparative 6 and Example 13 are summarized inTable 42 below. The concentrates for the first two were prepared at 22%H-FBS(EE) and 3% of either FES(EE)2 or FBS(EE)2 in aqueous ammoniumhydroxide, and then diluted in water to the state concentration. Theconcentrate for the latter example was prepared by dissolving 25%H-FBS(EEE) in aqueous ammonium hydroxide, and then diluted in water tothe stated concentrations.

TABLE 42 Surface Tension (dyn/cm)/Solubility of Neutral SurfactantBlends with H-FBS(EEE) H-FBS(EEE)/ H-FBS(EEE)/ Concentration FBS(EE)2FES(EE)2 H-FBS(EEE) (ppm) (Ex 25) (CE 6) (Ex 13) 1000 31.6/Yes 42.5/Yes39.9/Yes 2000 24.5/Yes 35.6/Yes 35.2/Yes 4000 21.0/Yes 29.8/Yes 31.4/Yes6000 20.5/Yes 27.8/Yes 29.2/Yes 8000 21.2/Yes 26.4/Yes 27.6/Yes

Surface tension results are significantly lower for H-FBS(EEE)/FBS(EE)2compared to H-FBS(EEE)/FES(EE)2 at equivalent concentrations. Thesurface tension results for H-FBS(EEE)/FES(EE)2 are essentially the sameas H-FBS(EEE) alone at equivalent total surfactant concentrations. Theaddition of the FBS(EE)2 significantly improves the surface tensionperformance, but the addition of FES(EE)2 has essentially no affect onthe surface tension of the solution. This indicates that the specificchoice of neutral surfactant additive is critical to the surface tensionperformance of such surfactant blends.

Solubility Test Results for Individual Neutral Surfactants in Water

Various neutral fluorinated surfactants were tested to determine theirsolubility in pure deionized water. Solubility test results aresummarized in Table 43. The solubility data indicate that neutralsurfactants of the present invention comprising oligomeric ethyleneoxide groups (identified by Roman numerals) generally provide superiorsolubility in water compared to similar art known neutral fluorinatedsurfactants (identified by letters of alphabet) lacking oligomericethylene oxide groups.

TABLE 43 Solubility for Neutral Fluorinated Surfactants in Water at 22°C. % Soluble in Structure # Compound Acronym water at 22 Deg C.* B(Comparative)

FBSEE  0.0592 V

FBSE(EE) 100    (miscible){circumflex over ( )} IV

FBS(EE)2  0.101 C (Comparative)

Me-FBSE**  0.118 VI

Me-FBSEE  0.232 *Neutral fluorinated surfactant samples saturated inwater were either filtered or phase split and the homogeneous aqueoussolutions were submitted for analysis via capillary gas chromatographyto determine their solubility in Water at 22° C. The analyses wereperformed using an Agilent 6890N gas chromatograph with a FlameIonization Detector (FID), an Agilent 7683A automatic sampler, and anHP-1, 30 m, 0.25 mm ID, 1 um df capillary column. Standards wereprepared between 0.1% (W/V) and 0.0001% (W/V) in Tetrahydrofuran (THF)stabilized with 0.025% (W/V) BHT [used as an internal standard] oracetonitrile. The samples were dissolved and diluted to 10% (W/V) instabilized THF or acetonitrile. {circumflex over ( )}Surfactant Samplewas found to dissolve at both 10% and 90% solids in water—completelymiscible with water. **Me-FBSE was prepared as described in U.S. Pat.No. 3,734,962

Other embodiments of the invention are within the scope of the appendedclaims.

1. A fluorinated sulfonamide surfactant composition comprising: aneutral surfactant according to the formula:R_(f)SO₂N[CH₂CH(CH₃)OH]₂;R_(f)SO₂N[CH₂CH(CH₃)OH][(CH₂CH₂O)_(n)H], where n is an integer from 1-6;orR_(f)SO₂N[(CH₂CH₂O)_(q)H][(CH₂CH₂O)_(m)H], where q is 1 or 2 and m is 2;and a solvent comprising water; wherein R_(f) is a fluoroalkyl grouphaving 3 to 8 carbon atoms.
 2. A composition according to claim 1,wherein the fluoroalkyl group is saturated.
 3. A composition accordingto claim 1, wherein the fluoroalkyl group is straight chain.
 4. Acomposition according to claim 1, wherein the fluoroalkyl group is aperfluoroalkyl group.
 5. A composition according to claim 1, wherein thefluoroalkyl group has 4 to 6 carbon atoms.
 6. A composition according toclaim 1, wherein the fluoroalkyl group is a saturated perfluoroalkylgroup having 4 to 6 carbon atoms.
 7. A composition according to claim 1,wherein the fluoroalkyl group is a saturated perfluoroalkyl group having4 carbon atoms.
 8. A method of treating a surface of a photoresistmaterial, the method comprising: exposing the photoresist material to acomposition according to claim 1.